Method for producing emulsifiable pesticide solutions

ABSTRACT

The current invention provides a kit of parts for producing an emulsifiable pesticide solution comprising: (a) a water miscible organic solvent selected from the list of a glycol ether, a glycerol formal, dimethylsulfoxide, gamma-butyrolactone or mixtures thereof, (b) an alkoxylated alcohol with an average of 6 to 80 moles of ethylene oxide and 2 to 60 moles of propylene oxide per mole of alcohol; and (c) a pesticidal active ingredient. The invention further provides a composition for producing an emulsifiable pesticide solution, a method for producing such a composition and a method for treating an agricultural crop. In addition the invention provides some advantageous pesticidal compositions.

CROSS REFERENCE TO RELATED APPLICATION

This application is a divisional of application Ser. No. 14/233,236,filed Jan. 16, 2014 and currently pending, which itself is a U.S.National Phase application under 35 U.S.C. §371 of InternationalApplication PCT/EP2012/064237, filed Jul. 19, 2012, which claimspriority to EP 11174573.3, filed Jul. 19, 2011.

TECHNICAL FIELD

The invention relates generally to the field of agricultural chemistry,and more specifically to the production of emulsifiable pesticidesolutions. In particular, the invention relates to a kit of parts and toa composition suitable for the production of a wide range of pesticideemulsifiable concentrates. The invention further relates to theemulsifiable concentrates derived thereof, and to the use of theemulsions obtained from adding the emulsifiable concentrates to waterfor the treatment of crops. In a final aspect the invention provides amethod for treating agricultural crops.

BACKGROUND

Agrochemical formulations are designed to make the product practical inuse and to obtain an evenly distribution of a small amount of activesubstance across a wide area for treatment of an agricultural crop. Whendeveloping a formulation, a number of factors need to be taken intoaccount: the type of application, the crop to be treated, regionalvariation in agronomical practice, and last but not leastphysical-chemical properties of the active substance, including meltingpoint, solubility and chemical stability.

Liquid formulations are preferred by the farmer for preparing spraysolutions for several reasons. They can be measured volumetrically, areeasy to handle, spontaneously form stable emulsions or dispersions and,given appropriate container design, are, usually easy to rinse out ofthe packaging. They are also easy to handle in bulk handling systems andgenerally do not cause application problems.

An emulsifiable concentrate consists of an active ingredient dissolvedin an organic solvent, with sufficient emulsifier added to create andoil-in-water emulsion after addition of water to the emulsifiableconcentrate. An emulsion is a mixture in which one liquid is suspendedin another liquid. In an agrochemical emulsion, water is often thecontinuous phase (carrier) while oil droplets consisting of solvent plusagrochemical active ingredient, are dispersed in it.

WO 2007/017501 discloses emulsifiable concentrate formulationscomprising a pesticide active ingredient, multicomponent solvent systemand multicomponent emulsifying system. All examples comprise an aromatichydrocarbon mixture.

The solvent for use in an emulsifiable concentrate is selected accordingto its capability of solubilizing a selected active ingredient. Thisrequirement is often fulfilled by aromatic and isoparaffinic solvents.However, the use of solvents with low flash points is becomingincreasingly restricted as governmental regulations are tightening theirtransportation and handling. Hence, there is a need to avoid the use offlammable solvents for the solubilization of active ingredient,especially for pesticidal active ingredients.

In order produce a concentrated emulsion, the emulsifier must becarefully selected to obtain a formulation in which a selectedagrochemical active ingredient is optimally distributed. To form stableconcentrated emulsions, irreversible anchoring in the oil droplet andstrong steric repulsion between particles are required. Irreversibleflocculation, or coalescence, of the emulsions is to be prevented bycreating an energy barrier that is sufficient to prevent the dropletsfrom approaching each other closely. Steric stabilization can beproduced using surfactants.

The demanding requirements outlined above result in products beingdeveloped for a specific active ingredient. This results in a largerange of products in storage at a formulation plant. Whereas productdevelopment for a new formulation takes a long period of time, demandfor just-in-time delivery in response to the onset diseases plant isincreasing. Formulators of agrochemicals are one the one hand faced withincreasing costs for raw materials and storage space, and on the otherhand with increasing complexity of agrochemical formulations.

EP 1625791 discloses a liquid insecticidal composition comprising amixture of dimethyl sulfoxide, gamma-butyrolactone and a propyleneoxide/ethylene oxide block copolymer surfactant in combination with achloronicotinyl compound.

U.S. Pat. No. 4,502,861 discloses a mothproofing formulation forapplication to keratinous materials comprising cypermethrin, abarbituric acid, diethylene glycol ethyl ether, amine or amidesurfactant, and a block copolymer of propylene glycol and ethyleneoxide.

WO 2007/017501 discloses an emulsifiable concentrate comprising aphenylsimicarbazone, a solvent system, one or more emulsifiers andoptionally further formulation additives for use against insect pests.

For none of the above formulations it was disclosed whether thesolvent/surfactant pair is compatible with other active ingredients, inparticular with a large number of diverse pesticidal active ingredients.

There remains a need in the art for improving the manufacturing processof agrochemical products and for emulsifiable pesticide solutions, inparticular for products with an improved environmental profile, that areeasy to manufacture, store and use, and are economically interesting toproduce.

The present invention aims to resolve or ameliorate at least some of theproblems mentioned above. In particular, the invention thereto aims toprovide emulsifiable pesticide solutions that are capable of reducingwarehouse costs whilst not restricting the formulator of providingfarmers with a broad product range of emulsifiable concentrates. Theemulsifiable concentrates are capable of providing good emulsionstability over an extended period at both elevated and freezingtemperatures. In addition the agrochemical formulations have a lowerenvironmental impact and are safer in use.

SUMMARY OF THE INVENTION

The present invention thereto provides a solvent/surfactant pairsuitable for combination with a large and diverse range of pesticidalactive ingredients to provide emulsifiable pesticide solutions.

In a first aspect, the current invention provides a kit of parts forproducing an emulsifiable pesticide solution comprising:

-   -   (a) a water miscible organic solvent selected from the list of a        glycol ether, a glycerol formal, dimethylsulfoxide,        gamma-butyrolactone or mixtures thereof,    -   (b) an alkoxylated alcohol with an average of 6 to 80 moles of        ethylene oxide and 2 to 60 moles of propylene oxide per mole of        alcohol; and    -   (c) a pesticidal active ingredient.

The present invention further relates to a composition for producingemulsifiable pesticide solutions obtained from said kit comprising: awater miscible organic solvent selected from the list of a glycol ether,a glycerol formal, dimethylsulfoxide, gamma-butyrolactone or mixturesthereof; and an alkoxylated alcohol with an average of 6 to 80 moles ofethylene oxide and 2 to 60 moles of propylene oxide per mole of alcohol.

The kit of parts and composition have the advantageous effect thatemulsifiable pesticide solutions can be obtained from it, in the absenceof an aromatic or isoparaffinic solvent. Avoidance of these flammablesolvents provides improved safety.

In a preferred embodiment of the invention, the solvent is dipropyleneglycol methyl ether, diethylene glycol monoethylether or dipropyleneglycol monoethyl ether.

In a preferred embodiment of the invention the alcohol alkoxylate is offormula (I) or (II), wherein x is between 2 and 22, y is between 6 and80; and z is between 2 and 60. More preferably x is between 2 and 14, yis between 10 and 60; and z is between 2 and 45.CH₃—(CH₂)_(x)—CH₂—O—(CH₂—CH₂—O)_(y)—(CH₂—CH(CH₃)—O)_(z)—H  (I)CH₃—(CH₂)_(x)—CH₂—O—(CH₂—CH(CH₃)—O)_(z)—(CH₂—CH₂—O)_(y)—H  (II)

In a preferred embodiment of the invention, the kit of parts orcomposition further comprise a pesticidal active ingredient selectedfrom the list of abamectin, alpha-cypermethrin, cypermethrin,permethrin, deltamethrin, diflubenzuron, flufenoxuron, ethofenprox,malathion, pymetrozin, pyriproxifen, azoxystrobin, chlorothalonil,cyprodinil, dimethomorph, dodine, iprodione, mancozeb, metconazole,spiroxamine, 2,4-dichlorophenoxyacetic acid, 2-ethylhexyl ester (2,4-DEHE), chloroprofam (CIPC), clethodim, metribuzin, prosulfocarb,pendimethalin, triclopyr buthoxyethyl ester, trinexapac-ethyl andmixtures thereof.

In a preferred embodiment of the invention, the selected pesticidalactive ingredient is a cypermethrin, an isomer of cypermethrin, ormixtures thereof; preferably the pesticidal active ingredient iscypermethrin.

The solvent/surfactant pair provided by the invention allows combinationwith a large and diverse range of pesticidal active ingredients toprovide emulsifiable concentrates.

In a preferred embodiment of the invention, the composition comprises

25-98%  diethylene glycol monoethyl ether, 1-15% alkoxylated alcohol offormula (I), 1-60% cypermethrin, 0-10% water, and 0-0.3%  antifoamingagent.

In another preferred embodiment of the invention, the composition forproducing emulsifiable pesticide solutions, comprises 250 g/ltrinexapac-ethyl, 150 g/l alkoxylated alcohol of formula (I) or (II) and550 g/l glycerol formal.

The emulsifying system of the present invention provides a systemcompatible with a large range of active ingredients. This isadvantageous as only a limited number of water-miscible solvents andsurfactants can be stored at a formulation plant, without restrictingthe range of commercial products that can be produced from therestricted number of raw materials. The term “surfactant” describes acompound, which can have the properties of emulsifying, dispersing orwetting agent.

In a further aspect, the invention provides a method for producingemulsifiable pesticide solutions comprising the steps of:

-   -   providing a solution comprising a water miscible organic solvent        selected from the list of a glycol ether, a glycerol formal,        dimethylsulfoxide, gamma-butyrolactone, or a combination        thereof; and a alkoxylated alcohol with an average of 6 to 80        moles of ethylene oxide and 2 to 60 moles of propylene oxide per        mole of alcohol,    -   adding to the solution a pesticidal active ingredient miscible        with the selected solvent.

In a preferred embodiment of the method, the method comprises the step:

-   -   warming the pre-emulsion comprising the pesticidal active        ingredient to a temperature between 20° C. to 60° C.

In a final aspect, the invention provides a method for treating anagricultural crop, comprising the steps of:

-   -   providing a kit of parts comprising    -   (a) a water miscible organic solvent selected from the list of a        glycol ether, a glycerol formal, dimethylsulfoxide,        gamma-butyrolactone or mixtures thereof,    -   (b) an alkoxylated alcohol with an average of 6 to 80 moles of        ethylene oxide and 2 to 60 moles of propylene oxide per mole of        alcohol; and    -   (c) a pesticidal active ingredient,    -   mixing (a) with (b) and (c) thereby providing a solution for        producing emulsifiable pesticide solutions,    -   adding the solution to water thereby emulsifying the pesticide        active ingredient and obtaining an emulsified pesticide        composition comprising an active ingredient in a pre-determined        dose rate,    -   applying the emulsified pesticide composition to an agricultural        crop suffering from a disease treatable with the selected active        ingredient and dose rate.

In a preferred embodiment of a method according to the invention, theactive ingredient is cypermethrin or trinexapac-ethyl.

In a method according to the invention, an emulsifiable agrochemical ismanufactured from a pre-emulsion comprising a combination of a solventand surfactant, wherein this combination was found to be compatible witha large number of agrochemical active ingredients. A method according toan embodiment of the invention thus allows a reduction of the inventoryat a formulation plant without having to compromise on the range ofproducts offered to farmers. Emulsified concentrates can be manufacturedon demand.

DETAILED DESCRIPTION OF THE INVENTION

Unless otherwise defined, all terms used in disclosing the invention,including technical and scientific terms, have the meaning as commonlyunderstood by one of ordinary skill in the art to which this inventionbelongs. By means of further guidance, term definitions are included tobetter appreciate the teaching of the present invention.

As used herein, the following terms have the following meanings:

“A”, “an”, and “the” as used herein refers to both singular and pluralreferents unless the context clearly dictates otherwise. By way ofexample, “a compartment” refers to one or more than one compartment.

“About” as used herein referring to a measurable value such as aparameter, an amount, a temporal duration, and the like, is meant toencompass variations of +/−20% or less, preferably +/−10% or less, morepreferably +/−5% or less, even more preferably +/−1% or less, and stillmore preferably +/−0.1% or less of and from the specified value, in sofar such variations are appropriate to perform in the disclosedinvention. However, it is to be understood that the value to which themodifier “about” refers is itself also specifically disclosed.

“Comprise,” “comprising,” and “comprises” and “comprised of” as usedherein are synonymous with “include”, “including”, “includes” or“contain”, “containing”, “contains” and are inclusive or open-endedterms that specifies the presence of what follows e.g. component and donot exclude or preclude the presence of additional, non-recitedcomponents, features, element, members, steps, known in the art ordisclosed therein.

The expression “% by weight” (weight percent), here and throughout thedescription unless otherwise defined, refers to the relative weight ofthe respective component based on the overall weight of the formulation.

The recitation of numerical ranges by endpoints includes all numbers andfractions subsumed within that range, as well as the recited endpoints.

The term “alkyl” refers to a straight or branched chain monovalenthydrocarbon radical having a specified number of carbon atoms. Alkylgroups may be unsubstituted or substituted with substituents that do notinterfere with the specified function of the composition. The carbonchain length may range from 6 to 18 carbon atoms.

The term “alkoxyl” refers to a straight or branched chain monovalenthydrocarbon radical having a specified number of carbon atoms and acarbon-oxygen-carbon bond, may be unsubstituted or substituted withsubstituents that do not interfere with the specified function of thecomposition.

The term “non-ionic” refers to a surface active compound, i.e. asurfactant, with one or more uncharged hydrophilic substituents thatdoes not generally dissociate as ions in a solution, distinguishablefrom anionic and cationic surfactants. The non-ionic surfactants areprimarily organic compounds having both hydrophilic and hydrophobicmoieties.

The inventors have found a composition which can act as a pre-emulsionfor a large number of agrochemical active ingredients. The compositioncomprises a water miscible organic solvent and a non-ionic surfactant.

The organic solvent is selected from the list of a glycol ether, aglycerol formal, dimethylsulfoxide, gamma-butyrolactone or a combinationthereof.

By the term “a glycol ether” as used herein, it is meant a compoundformed from a reaction of alkylene oxide with alcohols like methanol,ethanol, propanol, butanol or phenol. Subsequent reaction withadditional alkylene oxide leads to corresponding di-, tri- and higherglycol ethers. The reaction is typically catalyzed by a base.

Glycol ethers can be represented by the structural formula[CH3-CH2(OH)—CH2-O]n-R, wherein n=1, 2, or 3; and R=alkyl, preferablymethyl, ethyl, propyl or butyl.

Examples of ethylene glycol ethers are ethylene glycol monomethyl ether(2-methoxyethanol, CH₃OCH₂CH₂OH), ethylene glycol monoethyl ether(2-ethoxyethanol, CH₃CH₂OCH₂CH₂OH), ethylene glycol monopropyl ether(2-propoxyethanol, CH₃CH₂CH₂OCH₂CH₂OH), ethylene glycol monoisopropylether (2-isopropoxyethanol, (CH₃)₂CHOCH₂CH₂OH), ethylene glycolmonobutyl ether (2-butoxyethanol, CH₃CH₂CH₂CH₂OCH₂CH₂OH), ethyleneglycol monophenyl ether (2-phenoxyethanol, C₆H₅OCH₂CH₂OH), ethyleneglycol monobenzyl ether (2-benzyloxyethanol, C₆H₅CH₂OCH₂CH₂OH),diethylene glycol monomethyl ether (2-(2-methoxyethoxy)ethanol, methylcarbitol, CH₃OCH₂CH₂OCH₂CH₂OH), diethylene glycol monoethyl ether(2-(2-ethoxyethoxy)ethanol, carbitol cellosolve, CH₃CH₂OCH₂CH₂OCH₂CH₂OH)and diethylene glycol mono-n-butyl ether (2-(2-butoxyethoxy)ethanol,CH₃CH₂CH₂CH₂OCH₂CH₂OCH₂CH₂OH).

Diethylene glycol monoethyl ether is commercially available under thetrade name Carbitol.

Examples of propylene glycol ethers are propylene glycol n-butyl ether,dipropylene glycol n-butyl ether, dipropylene glycol methyl etheracetate, tripropylene glycol methyl ether, propylene glycol methylether, propylene glycol methyl ether acetate, dipropylene glycol methylether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether,dipropylene glycol methyl ether acetate and tripropylene glycol methylether.

In a preferred embodiment of a composition of the invention, the solventis dipropylene glycol methyl ether or diethylene glycol methyl ether.

Dipropylene glycol methyl ether is commercially available under thetrade name Dowanol DPM from the company Dow, US. Dipropylene glycol is ahydrophilic glycol ether with 100% water solubility at a temperature of25° C. It has a mid- to slow evaporating rate. For example, Dowanol DPMhas a relative evaporation rate of 0.03 (based on an arbitraryevaporation rate of butyl acetate of 1.0). It may be represented by theformula CH₃O[CH₂CH(CH₃)O]₂H (one of several isomers).

By the term “a glycerol formal” as used herein, it is meant acomposition consisting of 5-hydroxy-1,3-dioxane and4-hydroxymethyl-1,3-dioxolane, typically in a ratio of 60:40. It isprepared from glycerin and formaldehyde. The boiling point of glycerolformal is 191-195° C. at 760 mm Hg. Glycerol formal provides anenvironmentally-friendly alternative to aromatic solvents.

Dimethyl sulfoxide (DMSO) I san organosulfur compound with formula(CH₃)₂SO. This colorless liquid is an important polar aprotic solventthat is capable of dissolving both polar and nonpolar compounds. It ismiscible in a wide range of organic solvents as well as water.

Gamma-butyrolactone, abbreviated GBL, is a hygroscopic colorless oilyliquid which is soluble in water.

In another preferred embodiment the solvent is a 40:60 mixture ofdimethylsulfoxide and gammabutyrolactone. By the term “a 40:60 mixtureof dimethylsulfoxide and gamma-butyrolactone” as used herein, it ismeant a composition essentially comprising dimethylsulfoxide andgamma-butyrolactone in a ratio of 40 weight % dimethylsulfoxide to 60weight % gamma-butyrolactone.

These solvents are non-flammable, relatively cheap, easily pourable asof low viscosity, and of improved toxicological profile.

The inventors have found that a composition comprising a water miscibleorganic solvent selected from the list of a propylene glycol ether, aglycerol formal, dimethylsulfoxide, gamma-butyrolactone or a mixturethereof; and an alcohol alkoxylate derived from ethylene/propylene oxideunits, is particularly advantageous for producing emulsifiable pesticidesolutions. This combination of solvent and non-ionic surfactant wasfound to be compatible with a large range of pesticidal activeingredients.

Preferably the alkoxylated alcohol has an alkyl chain length of at least4 carbon atoms, preferably of 4 to 24 carbon atoms, more preferably of 4to 16 carbon atoms, most preferably of 12 to 15 carbon atoms. Thealkoxylated alcohol is preferably an alkoxylated fatty alcohol, meaningthe alcohol part has a carbon chain length of at least 8 carbon atoms.

The alkoxylated alcohol preferably has an average of 10 to 60 moles ofethylene oxide and 2 to 45 moles of propylene oxide per mole of alcohol;preferably 4 to 40 moles of propylene oxide per mole of alcohol.

The alkoxylated alcohol is preferably a block ethylene oxide/propyleneoxide adduct. More preferably the alkoxylated alcohol is a fattyalcohol/ethylene oxide/propylene oxide adduct.

Preferably the alkoxylated alcohol is a tri-block copolymer of fattyalcohol/ethylene oxide/propylene oxide or fatty alcohol/propyleneoxide/ethylene oxide of general formula (I) or (II)

wherein A is an alcohol moiety, R is a hydrocarbon chain of from 4 to 24carbon atoms, B represents ethylene oxide units and C representspropylene oxide units. The hydrophobic moiety R of the nonionic compoundmay be a primary or secondary, straight or branched alcohol having from4 to 24 carbon atoms. Preferably the number of carbon atoms in R is atleast 4, preferably between 4 and 15. R represents CH3-(CH2)x-Preferably x is between 3 and 14. y and z represent the average degreeof ethoxylation and propoxylation, respectively of 6 to 80 and 2 to 60.Preferably y is between 10 and 60, and z is between 2 and 45; preferablybetween 4 and 40.

The compounds represented by formula (I) and (II) can be obtained by thereaction of an alcohol with ethylene oxide and propylene oxide.Ethoxylations and propoxylations of alcohols are processes known to aperson skilled in the art.

The alcohol alkoxylate of formula (I) or (II), can be derived from analcohol described as ROH, wherein R is CH₃—(CH₂)_(x)—CH₂— and x isbetween 2 and 22. The alcohol may be butanol, hexanol, octanol, or afatty alcohol. Alkoxylation is preferably achieved by ethoxylation andpropoxylation.

The compound of formula (I) and (II) is preferably an alkoxylated fattyalcohol, more preferably an ethyoxylated and propoxylated blockco-polymer, more preferably an ethoxylated and propoxylated blockco-polymer of a fatty alcohol with carbon chain length of at least 4,preferably 4 to 15. Most preferably the compound of formula I is areaction product of a fatty alcohol with carbon chain length of at least4, preferably between 12 and 15, with 2 to 45 moles of propylene oxideand 10 to 60 moles of mole ethylene oxide.

They may be obtained by condensation of an alcohol containing from 4 to16 carbon atoms in a straight or branched chain configuration, condensedwith 10 to 60 moles of ethylene oxide and with 2 to 45 moles ofpropylene oxide.

Most preferably the compound alkoxylated alcohol is a tri-blockcopolymer of structure ABC or ACB, wherein A is the fatty alcohol, B ispolyethylene oxide and C is polypropylene oxide.

Preferably the minimum number average molecular weight of thealkoxylated alcohol, expressed in atomic mass units, is at least 1000,more preferably at least 1500, most preferably at least 2500.

Suitable ethoxylated/propoxylated fatty alcohols for use in theinvention may be commercially available in the product range under thetrade name Antarox, available from Rhodia; Surfonic LF, available fromHuntsman; Tergitol XD available from Dow; Synperonic PE, available fromBASF; Atlas G5000, available from Uniqema; Dehypon, available fromCognis; Tensiofix UNI01 and Tensiofix AGCA22 available from AjinomotoOmnichem.

More preferably the alkoxylated alcohol are α-alkyl-co-hydroxypoly(oxypropylene) and poly (oxyethylene) polymers where the alkyl chaincontains a minimum of four carbons and the minimum number averagemolecular weight, expressed in atomic mass units, is 1100.

Most preferably the alkoxylated alcohol are α-alkyl(C₁₂-C₁₅)-ω-hydroxypoly(oxypropylene)poly(oxyethylene)copolymers,wherein the poly(oxypropylene) content is 3-60 moles and thepoly(oxyethylene) content is 5-80 moles, the resulting ethoxylatedpropoxylated (C₁₂-C₁₅) alcohols having a minimum molecular weight,expressed in atomic mass units of 1500. Such a product can berepresented with the formulaCH₃—(CH₂)₁₀₋₁₃—CH₂—O—(CH₂—CH₂—O)₃₋₆₀—(CH(CH₃)—CH₂—O)₅₋₈₀—H. An exampleis represented by the compound with chemical abstract number CAS68551-13-3.

A composition according to an embodiment of the invention is compatiblewith a broad range of pesticide active ingredients. This allows reducingthe number of formulations and raw materials that have to be kept instock in order to be able to manufacture a broad range of emulsifiableconcentrates. This is cost effective.

The emulsifying system of the present invention is advantageous in thatonly few types of solvent miscible to water and surfactant need to bekept in stock at the production plant, allowing the manufacturing of alarge range of commercial products with a restricted number of rawmaterials.

By the term “compatible” as used herein, it is meant herein that noadverse effects occur as a result of mixing them together. Anincompatible mix can cause equipment damage, downtime, damage todesirable plants and chemical ineffectiveness. Incompatible mixes canresult from chemical or physical incompatibility. Chemicalincompatibility occurs when one or more of the chemicals changesproperties. Physical incompatibility causes the formation of lumps orgels. The chemicals do not disperse properly and settle out ofsuspension. Incompatibility can also take the form of foams,stratification in the tank, colour changes and bubbles.

By the term “active ingredient” as used herein, is meant an ingredientthat is chemically active and/or biologically active in origin. Theactivity is directed against a pest, particularly a plant pest. In thisregard an “active ingredient” ingredient can be a single ingredient or acombination of ingredients.

Active ingredients suitable for use in the present invention includeinsecticides such as abamectin, alpha-cypermethrin, cypermethrin,permethrin, deltamethrin, diflubenzuron, flufenoxuron, ethofenprox,malathion, pymetrozin, pyriproxifen, azoxystrobin, chlorothalonil,cyprodinil, dimethomorph, dodine, iprodione, mancozeb, metconazole,spiroxamine, 2,4-dichlorophenoxyacetic acid, 2-ethylhexyl ester (2,4-DEHE), chloroprofam (CIPC), clethodim, metribuzin, prosulfocarb,pendimethalin, triclopyr buthoxyethyl ester, and trinexapac-ethyl.

In a preferred embodiment of the composition, the composition furthercomprises a pesticidal active ingredient selected from the list ofabamectin, chlorpyriphos ethyl, a cypermethrin, deltamethrin,diflubenzuron, fenoxycarb, indoxacarb, malathion, pymetrozin,pyriproxifen; azoxystrobin, captan, chlorothalonil, cyprodinil,dimethomorph, dodine, folpet, fosetyl-aluminium, iprodione, mancozeb,metconazole, spiroxamine, 2,4-dichlorophenoxyacetic acid (2,4-D acid),2,4-dichlorophenoxyacetic acid, 2-ethylhexyl ester (2,4-D EHE),chloroprofam (CIPC), clethodim, glyphosate,2-methyl-4-chlorophenoxyacetic acid (MCPA), metribuzin, prosulfocarb,pendimethalin, triclopyr, gibberellic acid, maleic hydrazide andtrinexapac-ethyl.

In a preferred embodiment of the invention, the active ingredient istrinexapac-ethyl. This has for effect that solution will not freeze at atemperature of 4 to 5° C.

In a preferred embodiment, the composition comprising trinexapac-ethylas active ingredient is as follows:

Trinexapac-ethyl: 250 g/l

Tensiofix UNI 1: 150 g/l

Tensiofix D03: 200 g/l

Surfynol DF58: 2 g/l

Glycerol formal: 550 g/l

The Tensiofix D03 surfactant acts as biological activator. Thissurfactant is not necessary for the emulsion stability.

In a preferred embodiment of the composition, the selected pesticidalactive ingredient is a cypermethrin. By the term “a cypermethrin” asused herein it is meant, alpha-cypermethrin, cypermethrin,beta-cypermethrin, zeta-cypermethrin; and mixtures, derivatives orisomers thereof.

Cypermethrin is the ISO approved common name for(RS)-α-cyano-3-phenoxybenzyl(1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethyl cyclo propanecarboxylate. Cypermethrin is a synthetic pyrethroid insecticidecontaining three chiral centers, giving a racemic mixture of eightisomers comprising four diasterioisomeric pairs.

Alpha cypermethrin is a racemate consisting essentially of two of thefour cis isomers comprised in cypermethrin, in particular(S)-alpha-cyano-3-phenoxybenzyl(1R,3R)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylate and(R)-alpha-cyano-3-phenoxybenzyl(1S,3S)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylate.

Beta cypermethrin contains 4 of the 8 isomers which constitutecypermethrin. The isomers in beta-cypermethrin include 2 cis isomers(1S-cis-R and 1R-cis-S), which are the isomers contained inalpha-cypermethrin and 2 trans isomers (1S-trans-R and 1R-trans-S). Thecis isomers have a greater insecticidal activity than the trans isomers.

The term “zeta-cypermethrin” as used herein means(R,S)-α-cyano-3-phenoxybenzyl-(1RS)-cis-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylate.

In a more preferred embodiment of the invention, the selected pesticidalactive ingredient is cypermethrin.

In a more preferred embodiment of the invention, the selected pesticidalactive ingredient is cypermethrin, the surfactant is an alkoxylatedalcohol of formula (I) or (II) and the solvent is diethylene glycolmonoethyl ether.

Examples of such alcohols particularly include primary alcohols, whichmay be linear or branched, particularly mono-branched. The alkoxylationparts such alcohols are mixed ethoxylated/propoxylates which may beblock or random mixed alkoxylates, typically containing from 6 to 80moles of ethylene oxide and from 2 to 60 of propylene oxide, preferablywhere the polyalkoxylate chain is terminated with propylene oxide units.Preferably the polyoxyethylene/polyoxypropylene copolymers are blockcopolymers.

A preferred embodiment of the invention is a pesticidal compositionwherein cypermethrin is present in an amount of 1% to 60%, thealkoxylated alcohol of formula (I) is present in an amount of 1%-20%,and diethylene glycol monoethyl ether is present in an amount of25%-98%, wherein all the percentages are % by weight based upon thetotal weight of all the components in the composition. In addition thecomposition may comprise 0% to 10% water. An antifoaming agent may bepresent in the composition, in an amount of 0% to 0.3%.

In a preferred embodiment of the composition, the composition comprises:

50 wt % cypermethrin,

35% diethylene glycol monoethyl ether,

14.9 wt % alcohol/ethylene oxide/propylene oxide triblock copolymer, and

0.1% antifoaming agent.

In a preferred embodiment, the composition has a pH between 1 and 13,preferably the composition has a pH between 4 to 8, more preferably thepH of the composition is around 6.

The emulsifying system of the present invention provides a systemcompatible with a large range of active ingredients. This isadvantageous as only a limited number of water-miscible solvents andsurfactants can be stored at a formulation plant, without restrictingthe range of commercial products that can be produced from therestricted number of raw materials.

In a further aspect, the invention provides a method for the preparationof an emulsifiable pesticide solution and of an emulsified pesticidecomposition derived thereof.

A method according to an embodiment of the invention for producingemulsifiable pesticide solutions comprises the step of:

-   -   selecting a water miscible organic solvent from the list of a        glycol ether, a glycerol formal, dimethylsulfoxide,        gamma-butyrolactone, or mixtures thereof,    -   charging the solvent to a blending vessel,    -   adding to the selected solvent an alcohol alkoxylate of formula        (I), wherein x is between 2 and 14, y is between 6 and 80, and z        is between 2 and 60,    -   mixing the solvent and alcohol alkoxylate to obtain a        pre-emulsion for a pesticide active ingredient.

By the term “pre-emulsion” as used herein is meant, a compositionsuitable for the production of a pesticide emulsifiable concentrate.

The selection of the solvent is directed to the solubility of the activeingredient in the solvent.

The composition obtained as described above may serve as asolvent/surfactant pair for a broad range of pesticide activeingredients. To obtain a emulsifiable pesticide solution, a pesticidalactive ingredient miscible with the selected solvent/surfactant pair isadded to the pre-emulsion. The miscibility can be checked with astandard solubility screening test, known to a person skilled in theart. The emulsifiable pesticide solution thus obtained may be storedprior to its use for obtaining an emulsified pesticide solution.

The mixing can be carried out at room temperature or preferably at anelevated temperature. In a preferred embodiment of the method, themethod comprises the step of warming the solution comprising thepesticidal active ingredient to a temperature between 20° C. to 60° C.,preferably between 30° C. to 60° C.; more preferably around 40° C.Warming the mixture to a temperature of about 40° C. facilitates thedissolution of the pesticide.

In a preferred embodiment of the method, the method comprises the stepof adding the emulsifiable composition to water thereby obtaining anemulsified pesticide composition, and applying the emulsified pesticidecomposition to an agricultural crop for the treatment of a pesttreatable with the selected active ingredient.

The pesticide active ingredients may be used in the form of liquids orpowders. After mixing with the emulsifying system of the invention arepourable emulsifiable formulations which are readily dispersible inwater. The resulting emulsions are stable over time, typically in theorder of at least 4 hours. The finished product is not yet emulsified.When it is diluted with water, the emulsifiable composition will formthe emulsion. The emulsion is stable for at least 4 hours.

The pesticidal composition according to the invention is prepared bymixing the solvent miscible with the pesticidal composition atconcentration ranging from 10 g/l for the lowest concentration (forinstance in case of cypermethrin) until 800 g/l for the highestconcentration (for instance in case of triclopyr buthoxyethyl ester).

In a preferred embodiment a composition of the invention is used for thetreatment of agricultural crops.

In a final aspect, the invention provides a method for treating anagricultural crop, comprising the steps of:

-   -   providing a kit of parts comprising    -   (a) a water miscible organic solvent selected from the list of a        glycol ether, a glycerol formal, dimethylsulfoxide,        gamma-butyrolactone or mixtures thereof,    -   (b) an alkoxylated alcohol with an average of 6 to 80 moles of        ethylene oxide and 2 to 60 moles of propylene oxide per mole of        alcohol; and    -   (c) a pesticidal active ingredient,    -   mixing (a) with (b) and (c) thereby providing a solution for        producing emulsifiable pesticide solutions,    -   adding water to the solution thereby emulsifying the pesticide        active ingredient and obtaining an emulsified pesticide        composition comprising an active ingredient in a pre-determined        dose rate,    -   applying the emulsified pesticide composition to an agricultural        crop suffering from a disease treatable with the selected active        ingredient and dose rate.

In a preferred embodiment the kit of parts is accompanied with aninformation leaflet providing instructions to combine the solvent,surfactant and pesticidal active ingredient to obtain an emulsifiablepesticide solution. The product leaflet may specify the concentrationsof the ingredients to be used. It may also provide specific examples ofcompositions.

The present invention will be now described in more details, referringto examples that are not limitative. It is supposed that the presentinvention is not restricted to any form of realization describedpreviously and that some modifications can be added to the presentedexample of fabrication without reappraisal of the appended claims.

EXAMPLES Example 1

In the experiment summarized in Table 1, emulsifiable pesticidesolutions were prepared starting from a kit of parts comprising DMSO40%+GBL 60%, Tensiofix UNI01 and a selection out of a group of activeingredients. First, the solvent DMSO40/GBL60 was mixed with a non-ionicsurfactant, in particular with Tensiofix UNI01. The mixture obtained wasdivided into several samples. To the samples a selected activeingredient was added. The emulsifiable pesticide solution thus obtainwas inspected for emulsion stability. It was observed if a homogenousmixture was obtained and if no visible amounts of pesticide settled.

TABLE 1 Summary of experiment of Example 1 Emulsion 1% v/v Activeingredient (g/l) Surfactant (g/l) Solvent CIPAC D water 20° C.Difenoconazole 250 Tensiofix UNI01 150 Mix GBL/DMSO to 1 L no oily phase40/60 Imazalil 100 Tensiofix UNI01 150 Mix GBL/DMSO to 1 L no oily phase40/60 Triclopyr 800 Tensiofix UNI01 100 Mix GBL/DMSO to 1 L no oilyphase 40/60 Prosulfocarb 500 Tensiofix UNI01 100 Mix GBL/DMSO to 1 L nooily phase 40/60 CIPC 100 Tensiofix UNI01 150 Mix GBL/DMSO to 1 L nooily phase 40/60 Cypermethrin + 60 + Tensiofix UNI01 150 Mix GBL/DMSO to1 L no oily phase PBO 171 40/60 Trinexapac-ethyl 250 Tensiofix UNI01 150Mix GBL/DMSO to 1 L no oily phase 40/60 Pyriproxifen 100 Tensiofix UNI01150 Mix GBL/DMSO to 1 L no oily phase 40/60 Permethrin 250 TensiofixUNI01 150 Mix GBL/DMSO to 1 L no oily phase 40/60

In Examples 2 to 4 further examples of emulsifiable compositions areprovided. To obtain an emulsion concentrate, water is added to thecomposition.

Example 2

Cypermethrin: 50%

Tensiofix UNI01: 14.9%

Surfynol DF58 (antifoam): 0.1%

Carbitol: 35%

Example 3

Cypermethrin: 10%

Dowanol DPM: 82%

Tensiofix UNI01: 4%

Water: 4%

Example 4

Spiroxamine: 50%

Dowanol DPM: 35%

Tensiofix UNI01: 15%

Example 5

In the following experiment pesticidal compositions were preparedcomprising different solvent surfactant pairs. These includesolvent/surfactant pairs according to the invention (Refs 2-4) andothers. The respective compositions are provided in the colums activeingredient/surfactant/solvent/other. The amount of ingredients used isalso indicated. After constitution of the formulas, the aspect of thefinal product was visually observed and noted down. The result isreflected in the column final product aspect. The formulations were usedto prepare emulsions as in previous examples, 1% v/v. After 1 hour the1% emulsions were again observed and the result noted down in the columnemulsion stability. The results were photographed.

Pluronic PE 10400 is an EO/PO block co-polymer, in particular an ABAblock co-polymer containing 25 moles of ethylene oxide, 56 moles ofpropylene oxide and 25 moles of ethylene oxide providing the chemicalstructure EO₂₅PO₅₆EO₂₅.

Synperonic PE/P105 is an EO/PO block co-polymer, in particular, an ABAblock-co-polymer containing 37 moles of ethylene oxide (EO), 56 moles ofpropylene oxide (PO) and 37 moles of ethylene oxide (EO) providing thechemical structure EO₃₇PO₅₆EO₃₇.

Genapol EP 0244 is an alcohol alkoxylate, in particular a C10/C12alcohol with 4 EO followed by 4 PO.

Tensiofix UNI01 is an alcohol alkoxylate with an average of 6 to 80moles of ethylene oxide and 4 to 60 moles of propylene oxide per mole ofalcohol.

As can be seen from the results reported in Tables 2-4, formulas with asolvent/surfactant pair according to the invention provided homogeneousand stable emulsions. Formation of sediment was not observed after 1hour in CIPAC D water at 20° C.

For other solvent/surfactant pairs, wherein the solvent was kept thesame and the surfactant was similar, a homogenous emulsion withoutsediment formation or crystallization could not be obtained.

TABLE 2 comparative examples of emulsifiable cypermethrin solutions, andemulsions obtainable thereof Final Emulsion 1% v/v- Active product Selfstability after 1 hour in Formula ingredient g/l Surfactant g/l Solventg/l Other g/l aspect emulsification CIPAC D water at 20° C. 4Cypermethrin 500 Pluronic PE 149 Carbitol To 1 L Surfynol 1 LimpidHomogeneous 0.5 ml sediment technical 10400 DF58 liquid in the bottomgrade Dark yellow 5 Cypermethrin 500 Genapol EP 149 Carbitol To 1 LSurfynol 1 Limpid Non- Formula has technical 0204 DF58 liquidhomogeneous agglomerate in the grade Dark bottom Suspended yellowagglomerates 6 Cypermethrin 500 Synperonic 149 Carbitol To 1 L Surfynol1 Limpid Non- 0.5 ml of sediment technical PE/P 105 DF58 liquidhomogeneous grade Yellow Ref 2 Cypermethrin 500 Tensiofix 149 CarbitolTo 1 L Surfynol 1 Limpid Homogeneous Homogenous (embodiment technicalUNI 01 DF58 liquid invention) grade Pale yellow

TABLE 3 comparative examples of prosulfocarb solutions, and emulsionsobtainable thereof Final Emulsion 1% v/v - Active product Self stabilityafter 1 hour in Formula ingredient g/l Surfactant g/l Solvent g/l aspectemulsification CIPAC D water at 20° C. 7 Prosulfocarb 500 Pluronic PE100 GBL40/ To 1 L Limpid Non- 2 ml sediment Technical 10400 DMSO 60liquid homogenous grade Light Flakes yellow 8 Prosulfocarb 500 Genapol100 GBL40/ To 1 L Limpid Non- Non- Technical EP0204 DMSO 60 liquidhomogeneous homogeneous grade Light Oily spheres yellow going down 9Prosulfocarb 500 Synperonic 100 GBL40/ To 1 L Limpid Non- 1.7 mlsediment Technical PE/P 105 DMSO 60 liquid homogeneous grade Lightyellow Ref 3 Prosulfocarb 500 Tensiofix 100 GBL40/ To 1 L LimpidHomogeneous Homogenous (embodiment Technical UNI01 DMSO 60 liquidinvention) grade Yellow

TABLE 4 comparative examples of emulsifiable pyriproxifen solutions, andemulsions obtainable thereof Final Emulsion 1% v/v - Active product Selfstability after 1 hour in Formula ingredient g/l Surfactant g/l Solventg/l aspect emulsification CIPAC D water at 20° C. 10 Pyriproxifen 100Pluronic PE 100 GBL40/ To 1 L Limpid Homogeneous 3 ml sediment Technical10400 DMSO 60 liquid grade Colourless 11 Pyriproxifen 100 Genapol 100GBL40/ To 1 L Limpid Homogeneous Small crystals on Technical EP0204 DMSO60 liquid the bottom grade Colourless 12 Pyriproxifen 100 Synperonic 100GBL40/ To 1 L Limpid Homogeneous 1.8 ml sediment Technical PE/P 105 DMSO60 liquid grade Colourless Ref 4 Pyriproxifen 100 Tensiofix 100 GBL40/To 1 L Limpid Homogeneous Homogenous (embodiment Technical UNI01 DMSO 60liquid invention) grade Colourless

What is claimed is:
 1. Composition for producing emulsifiable pesticidesolutions comprising: (a) a water miscible organic solvent selected fromthe group consisting of a glycol ether, a glycerol formal,dimethylsulfoxide, gamma-butyrolactone and mixtures thereof; and (b) analkoxylated alcohol, (c) a pesticidal active ingredient, wherein thealkoxylated alcohol is of formula (II),CH3-(CH₂)_(x)—CH₂—O—(CH₂—CH(CH₃)—O)_(z)—(CH₂—CH₂—O)_(y)—H  (II) whereinx is between 10 and 13, y is between 10 and 60; and z is between 2 and45; and the minimum number average molecular weight of the alkoxylatedalcohol, expressed in atomic mass units, is at least
 1000. 2.Composition according to claim 1, comprising: 25-98%  diethylene glycolmonoethyl ether, 1-20% alkoxylated alcohol, 1-60% cypermethrin, 0-10%water, and 0-0.3%  antifoam.


3. Composition according to claim 1, wherein the solvent is dipropyleneglycol methyl ether, diethylene glycol monoethylether or dipropyleneglycol monoethyl ether.
 4. Composition according to claim 1, wherein thepesticidal active ingredient is selected from the list of abamectin,alpha-cypermethrin, cypermethrin, permethrin, deltamethrin,diflubenzuron, flufenoxuron, ethofenprox, malathion, pymetrozin,pyriproxifen, azoxystrobin, chlorothalonil, cyprodinil, dimethomorph,dodine, iprodione, mancozeb, metconazole, spiroxamine,2,4-dichlorophenoxyacetic acid, 2-ethylhexyl ester (2,4-D EHE),chloroprofam (CIPC), clethodim, metribuzin, prosulfocarb, pendimethalin,triclopyr buthoxyethyl ester, trinexapac-ethyl, and a mixture thereof.5. Composition according to claim 1, wherein the selected pesticidalactive ingredient is a cypermethrin, an isomer of cypermethrin, ormixtures thereof.
 6. Composition according to claim 5, wherein thepesticidal active ingredient is cypermethrin.
 7. Composition accordingto claim 1, wherein the selected pesticidal active ingredient istrinexapac-ethyl.
 8. Kit of parts for producing an emulsifiablepesticide solution comprising: (a) a water miscible organic solventselected from the group consisting of a glycol ether, a glycerol formal,dimethylsulfoxide, gamma-butyrolactone and mixtures thereof, (b) analkoxylated alcohol; and (c) a pesticidal active ingredient, wherein thealkoxylated alcohol is of formula (II),CH3-(CH₂)_(x)—CH₂—O—(CH₂—CH(CH₃)—O)_(z)—(CH₂—CH₂—O)_(y)—H  (II) whereinx is between 10 and 13, y is between 10 and 60; and z is between 2 and45; and the minimum number average molecular weight of the alkoxylatedalcohol, expressed in atomic mass units, is at least
 1000. 9. Kit ofparts according to claim 8, wherein the solvent is dipropylene glycolmethyl ether, diethylene glycol monoethylether or dipropylene glycolmonoethyl ether.
 10. Kit of parts according to claim 8, wherein thepesticidal active ingredient is selected from the list of abamectin,alpha-cypermethrin, cypermethrin, permethrin, deltamethrin,diflubenzuron, flufenoxuron, ethofenprox, malathion, pymetrozin,pyriproxifen, azoxystrobin, chlorothalonil, cyprodinil, dimethomorph,dodine, iprodione, mancozeb, metconazole, spiroxamine,2,4-dichlorophenoxyacetic acid, 2-ethylhexyl ester (2,4-D EHE),chloroprofam (CIPC), clethodim, metribuzin, prosulfocarb, pendimethalin,triclopyr buthoxyethyl ester, trinexapac-ethyl, and a mixture thereof.11. Kit of parts according to claim 8, wherein the selected pesticidalactive ingredient is a cypermethrin, an isomer of cypermethrin, ormixtures thereof.
 12. Kit of parts according to claim 11, wherein thepesticidal active ingredient is cypermethrin.
 13. Kit of parts accordingto claim 8, wherein the selected pesticidal active ingredient istrinexapac-ethyl.